Wednesday, November 7, 2007 - 5:30 PM
469i

Investigation Of Charge-Transfer Atomic Potentials Using Evolutionary Strategies And Molecular Dynamics Simulations

Brian C. Barnes and Lev D. Gelb. Department of Chemistry, Washington University in St. Louis, One Brookings Drive, St. Louis, MO 63130

The development and performance of charge-transfer potentials for water and silica sol-gel systems is considered. Charge-transfer potentials allow for redistribution of charge between atoms and therefore can describe their behavior with changes in local chemical environment; such behavior is critical to correct description of, for instance, the dissociation of water into hydroxide and hydronium ions. Parameterization of a complete potential using both charge-transfer functions and traditional two- and three-body empirical potential terms is a challenging numerical problem. Evolutionary Strategy (ES) optimizations were used to fit various charge-transfer potentials against first-principles data. Evolutionary strategies are similar to genetic algorithms in that they use parameter recombination and mutation in many simultaneous trial solutions with a competitive, generation-based search. Since there are many possible ES algorithms that could be used for such work, we first evaluated the efficiency of various evolutionary strategies in fitting two- and three-body empirical potentials for aqueous silicate systems against a ``training set'' of configurational energies. Finally, the performance of charge-transfer potentials in modeling pure water and the initial steps of silicic acid gelation is compared with that of the Feuston-Garofalini potential [J. Phys. Chem., 94, 5351 (1990)] and other recent models.